Silver halide color photographic light-sensitive material

ABSTRACT

A silver halide color photographic light-sensitive material which comprises a support having thereon at least one silver halide emulsion layer containing dispersed therein at least one magenta coupler represented by the following general formula (I): ##STR1## wherein R 1  and R 2 , which may be the same or different, each represents a hydrogen atom or a substituent, each represents a hydrogen atom or a substituent, X represents a hydrogen atom or a group capable of being eliminated upon coupling with an oxidation product of an aromatic primary amine developing agent, Z represents a nitrogen atom or --CR 6  where R 6  represents a hydrogen atom or a substituent and dimers or higher polymers thereof, 
     together with at least one high boiling organic solvent represented by the following general formula (II): ##STR2## wherein R 3 , R 4  and R 5 , which may be the same or different, each represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, provided that the total number of carbon atoms contained in the groups represented by R 3 , R 4  and R 5  is 12 to 60.

FIELD OF THE INVENTION

This invention relates to a silver halide color photographiclight-sensitive material and, more particularly, to a silyer halidecolor photographic light-sensitive material having improved colorreproducibility and color image fastness.

BACKGROUND OF THE INVENTION

In silver halide color photographic light-sensitive materials, silverhalide emulsions and so-called dye forming couplers (hereinafter merelyreferred to as couplers) capable of reacting with an oxidation productof an aromatic primary amine developing agent are often employed. Inparticular, a combination of a yellow coupler, a cyan coupler and amagenta coupler is usually employed in color photographiclight-sensitive materials.

Of these, 5-pyrazolone type couplers widely used as magenta couplershave serious problems in color reproduction, since they show a sideabsorption around 430 nm and show a poor toe cut of absorption on thelonger wavelength side.

In order to solve these problems, pyrazoloazole type magenta couplershave been developed. Magenta dyes obtained by coupling this type ofcoupler with an oxidation product of an aromatic primary aminedeveloping agent do not have a side absorption around 430 nm as an ethylacetate solution, and provide a very pure magenta color with a good toecut of absorption on the longer wavelength side.

However, problems exist with these couplers in that the images formed onfilm or photographic printing paper by imagewise exposure and colordeveloping light-sensitive materials which have silver halide emulsionlayers containing these pyrazoloazole type magenta couplers dispersedtherein using a high boiling organic solvent do not necessarily exhibita good toe cut on the longer wavelength side in the reflectionabsorption spectrum. Further, these couplers fail to sufficientlyimprove color reproducibility, and possess only insufficient color imagelight fastness.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a silver halide colorphotographic light-sensitive material having an improved colorreproducibility which is attained by forming a magenta color image witha good hue and a sharp toe cut of absorption on the longer wavelengthside using a pyrazoloazole type coupler.

Another object of the present invention is to provide a silver halidecolor photographic light-sensitive material having an improved colorimage fastness using a pyrazoloazole coupler.

These and other objects of the present invention will become apparentfrom the following description thereof.

The above-described and other objects of the present invention areattained by a silver halide color photographic light-sensitive materialwhich comprises a support having thereon at least one silver halideemulsion layer containing dispersed therein at least one magenta couplerrepresented by the following general formula (I): ##STR3## wherein R¹and R², which may be the same or different, each represents a hydrogenatom or a substituent, X represents a hydrogen atom or a group capableof being eliminated on coupling with an oxidation product of an aromaticprimary amine developing agent, Z represents a nitrogen atom or -CR⁶where R⁶ represents a hydrogen atom or a substituent, and the couplermay form a dimer or higher polymer at R¹, R², R⁶ or X

together with at least one high boiling organic solvent represented bythe following general formula (II): ##STR4## wherein R³, R⁴ and R⁵,which may be the same or different, each represents an alkyl group, acycloalkyl group, an alkenyl group or an aryl group, provided that thetotal number of carbon atoms contained in the groups represented by R³,R⁴ and R⁵ is 12 to 60.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 and 2 show absorption spectra of magenta color dyes. In FIG. 1,the absorption spectrum for Comparative Example 2 almost overlaps thatof Comparative Example 3 on the shorter wavelength side with respect tothe absorption maximum. In FIG. 2, A, B and D almost overlap one anotheron the shorter wavelength side with respect to the absorption maximum.

DETAILED DESCRIPTION OF THE INVENTION

In the general formula (I), the term "a dimer or a higher polymer" meanstwo or more groups represented by the general formula (I) are present ineach molecule, including bis derivatives and polymer couplers. Thepolymer couplers may be homopolymers comprising one or more monomershaving the moiety represented by the general formula (I) (preferablyhaving an ethylenically unsaturated group) or may be copolymers of atleast one such monomer with at least one ethylenically unsaturatedmonomer which does not couple with an oxidation product of an aromaticprimary amine developing agent and, therefore, does not form a colordye.

Examples of compounds, represented by the general formula (I) include1H-imidazo[1,2-b]pyrazoles and 1H-pyrazolo[1,5-b][1,2,4]triazoles, whichare respectively represented by the following general formulae (III) and(IV). Of these, those compounds which are represented by the generalformula (IV) are particularly preferable. ##STR5##

R¹, R² and R⁶ in the general formulae (III) and (IV), which can be thesame or different, each represents a hydrogen atom or a substituent. Thesubstituent includes a halogen atom, an alkyl group, an aryl group, aheterocyclic group, a cyano group, an alkoxy group, an aryloxy group, aheterocyclic oxy group, an acyloxy group, a carbamoyloxy group, asilyloxy group, a sulfonyloxy group, an acylamino group, an anilinogroup, a ureido group, an imido group, a sulfamoylamino group, acarbamoylamino group, an alkylthio group, an arylthio group, aheterocyclic thio group, an alkoxycarbonylamino group, anaryloxycarbonylamino group, a sulfonamido group, a carbamoyl group, anacyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, analkoxycarbonyl group and an aryloxycarbonyl group. X represents ahydrogen atom or a group capable of being eliminated upon coupling withan aromatic primary amine developing agent which includes a halogenatom, a carboxy group, or an another coupling-off group bound to thecarbon atom in the coupling position through an oxygen atom, a nitrogenatom or a sulfur atom.

R¹, R² R⁶ or X also may be a divalent group to form a bis derivative. Inaddition, where the moiety represented by the general formula (III) or(IV) exists in a vinyl monomer, R¹, R² or R⁶ represents a bond or alinking group through which the moiety represented by the generalformula (III) or (IV) and an ethylenically unsaturated group are boundto each other.

More particularly, R¹, R² and R⁶ each represents a hydrogen atom, ahalogen atom (e.g., a chlorine atom, a bromine atom, etc.), an alkylgroup (e.g., a methyl group, a propyl group, a, t-butyl group, atrifluoromethyl group, a tridecyl group, a3-(2,4-di-t-amylphenoxy)propyl group, a 2-dodecyloxyethyl group, a3-phenoxypropyl group, a 2-hexylsulfonylethyl group, a cyclopentylgroup, a benzyl group, etc.), an aryl group (e.g., a phenyl group, a4-t-butylphenyl group, a 2,4-di-t-amylphenyl group, a4-tetradecanamidophenyl group, etc.), a heterocyclic group (e.g., a2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a2-benzothiazolyl group, etc.), a cyano group, an alkoxy group (e.g., amethoxy group, an ethoxy group, a 2-methoxyethoxy group, a2-dodecyloxyethoxy group, a 2-methanesulfonylethoxy group, etc.), anaryloxy group (e.g., a phenoxy group, a 2-methylphenoxy group, a4-t-butylphenoxy group, etc ), a heterocyclic oxy group (e.g., a2-benzimidazolyloxy group, etc.), an acyloxy group (e.g., an acetoxygroup, a hexadecanoyloxy group, etc.), a carbamoyloxy group (e.g., anN-phenylcarbamoyloxy group, an N-ethylcarbamoyloxy group, etc.), asilyloxy group (e.g., a trimethylsilyloxy group, etc.), a sulfonyloxygroup (e.g., a dodecylsulfonyloxy group, etc.), an acylamino group(e.g., an acetamido group, a benzamido group, a tetradecanamido group,an α-(2,4-di-t-amylphenoxy-)-butyramido group, aγ-(3-t-butyl-4-hydroxyphenoxy)-butyramido group, anα-[4-(4-hydroxyphenylsulfonyl)-phenoxy]decanamido group, etc.), ananilino group (e.g., a phenylamino group, a 2-chloroanilino group, a2-chloro-5-tetradecanamidoanilino group, a2-chloro-5-dodecyloxycarbonylanilino group, an N-acetylanilino group, a2-chloro-5-[α-(3-t-butyl-4-hydroxyphenoxy)dodecanamido]-anilino group,etc.), a ureido group (e.g., a phenylureido group, a methylureido group,an N,N-dibutylureido group, etc.), an imido group (e.g., anN-succinimido group, a 3-benzylhydantoinyl group, a4-(2-ethylhexanoylamino)phthalimido group, etc.), a sulfamoylamino group(e.g., an N,N-dipropylsulfamoyl group, an N-methyl-N-decylsulfamoylaminogroup, etc.), an alkylthio group (e.g., a methylthio group, an octylthiogroup, a tetradecylthio group, a 2-phenoxyethylthio group, a3-phenoxypropylthio group, a 3-(4-t-butylphenoxy)propylthio group,etc.), an arylthio group (e.g., a phenylthio group, a2-butoxy-5-t-octylphenylthio group, a 3-pentadecylphenylthio group, a2-carboxyphenylthio group, a 4-tetradecanamidophenylthio group, etc.), aheterocyclic thio group (e.g., a 2-benzothiazolylthio group, etc.), analkoxycarbonylamino group (e.g., a methoxycarbonylamino group, atetradecyloxycarbonylamino group, etc.), an aryloxycarbonylamino group(e.g., a phenoxycarbonylamino group, a2,4-di-tert-butylphenoxycarbonylamino group, etc.), a sulfonamido group(e.g., a methanesulfonamido group, a hexadecanesulfonamido group, abenzenesulfonamido group, a p-toluenesulfonamido group, anoctadecanesulfonamido group, a 2-methyloxy-5-t-butylbenzenesulfonamidogroup, etc.), a carbamoyl group (e.g., an N-ethylcarbamoyl group, anN,N-dibutylcarbamoyl group, an N-(2-dodecyloxyethyl)-carbamoyl group, anN-methyl-N-dodecylcarbamoyl group, anN-[3-(2,4-di-tert-amylphenoxy)propyl]carbamoyl group, etc.), an acylgroup (e.g., an acetyl group, a (2,4-di-tert-amylphenoxy)acetyl group, abenzoyl group, etc.), a sulfamoyl group (e.g., an N-ethylsulfamoylgroup, an N,N-dipropylsulfamoyl group, anN-(2-dodecyloxyethyl)-sulfamoyl group, an N-ethyl-N-dodecylsulfamoylgroup, an N,N-diethylsulfamoyl group, etc.), a sulfonyl group (e.g., amethanesulfonyl group, an octanesulfonyl group, a benzenesulfonyl group,a toluenesulfonyl group, etc.), a sulfinyl group (e.g., anoctanesulfinyl group, a dodecylsulfinyl group, a phenylsulfinyl group,etc.), an alkoxycarbonyl group (e.g., a methoxycarbonyl group, abutyloxycarbonyl group, a dodecylcarbonyl group, an octadecylcarbonylgroup, etc.) or an aryloxycarbonyl group (e.g., a phenyloxycarbonylgroup, a 3-pentadecyloxycarbonyl group, etc.), and X represents ahydrogen atom, a halogen atom (e.g., a chlorine atom, a bromine atom, aniodine atom, etc.), a carboxyl group, a group bound via an oxygen atom(e.g., an acetoxy group, a propanoyloxy group, a benzoyloxy group, a2,4-dichlorobenzoyloxy group, an ethoxyoxaloyloxy group, a pyruvinyloxygroup, a cinnamoyloxy group, a phenoxy group, a 4-cyanophenoxy group, a4-methanesulfonamidophenoxy group, a 4-methanesulfonylphenoxy group, anα-naphthoxy group, a 3-pentadecylphenoxy group, a benzyloxycarbonyloxygroup, an ethoxy group, a 2-cyanoethoxy group, a benzyloxy group, a2-phenethyloxy group, a 2-phenoxyethoxy group, a 5-phenyltetrazolyloxygroup, a 2-benzothiazolyloxy group, etc.), a group bound via a nitrogenatom (e.g., a benzenesulfonamido group, an N-ethyltoluenesulfonamidogroup, a heptafluorobutanamido group, a 2,3,4,5,6-pentafluorobenzamidogroup, an octanesulfonamido group, a p-cyanophenylureido group, anN,N-diethylsulfamoylamino group, a 1-piperidyl group, a5,5-dimethyl-2,4-dioxo-3-oxazolidinyl group, a1-benzylethoxy-3-hydantoinyl group, a2N-1,1-dioxo-3(2H)-oxo-1,2-benzoisothiazolyl group, a2-oxo-1,2-dihydro-1-pyridinyl group, an imidazolyl group, a pyrazolylgroup, a 3,5-diethyl-1,2,4-triazol-1-yl group, a 5- or6-bromobenzotriazol-1-yl group, a 5-methyl-1,2,3,4-triazol-1-yl group, abenzimidazolyl group, a 3-benzyl-1-hydantoinyl group, a1-benzyl-5-hexadecyloxy-3-hydantoinyl group, a 5-methyl-1-tetrazolylgroup, a 4-methoxyphenylazo group, a 4-pivaloylaminophenylazo group, a2-hydroxy-4-propanoylphenylazo group, etc.), or a group bound via asulfur atom (e.g., a phenylthio group, a 2-carboxyphenylthio group, a2-methoxy-5-t-octylphenylthio group, a 4-methanesulfonylphenylthiogroup, a 4-octanesulfonamidophenylthio group, a 2-butoxyphenylthiogroup, a 2-(2-hexanesulfonylethyl)-5-tertoctylphenylthio group, abenzylthio group, a 2-cyanoethylthio group, a1-ethoxycarbonyltridecylthio group, a 5-phenyl-2,3,4,5-tetrazolylthiogroup, a 2-benzothiazolylthio group, a 2-dodecylthio-5-thiophenylthiogroup, a 2-phenyl-3-dodecyl-1,2,4-triazolyl-5-thio group, etc.).

Where R¹, R² R⁶ or X represents a divalent group to form a bisderivative, such divalent group includes a substituted or unsubstitutedalkylene group (e.g., a methylene group, an ethylene group, a1,10-decylene group, -CH₂ CH₂ -O-CH₂ CH₂ -, etc.), a substituted orunsubstituted phenylene group (e.g., a 1,4-phenylene group, a1,3-phenylene group ##STR6## (etc.), or -NHCO-R₇ -CONH- (wherein R₇represents a substituted or unsubstituted alkylene or phenylene group).

Where the moiety represented by the general formula (III) or (IV) existsin a vinyl monomer, the linking group represented by R¹, R² or R⁶includes an alkylene group (a substituted or unsubstituted alkylenegroup, e.g., a methylene group, an ethylene group, a 1,10-decylenegroup, -CH₂ CH₂ OCH₂ CH₂ -, etc.), a phenylene group (a substituted orunsubstituted phenylene group, e.g., a 1,4-phenylene group, a1,3-phenylene group ##STR7## (etc.), -NHCO-, -CONH-, -O-, -OCO-, or anaralkylene group (e.g., ##STR8## (etc.) alone or in combination thereof.

Additionally, the ethylenically unsaturated group in the vinyl monomerincludes those which have other substituents than are represented by thegeneral formulae (III) and (IV). Preferred substituents are a hydrogenatom, a chlorine atom or a lower alkyl group containing 1 to 4 carbonatoms.

Illustrative examples of ethylenically unsaturated monomers which do notcouple with an oxidation product of an aromatic primary amine developingagent and therefore do not form a color dye include acrylic acid,α-chloroacrylic acid, α-alacrylic acids (e.g., methacrylic acid, etc.),esters or amides derived from these acrylic acids (e.g., acrylamide,n-butylacrylamide, t-butylacrylamide, diacetoneacrylamide,methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate,n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, 2-ethylhexylacrylate, n-octyl acrylate, lautyl acrylate, methyl methacrylate, ethylmethacrylate, n-butyl methacrylate and β-hydroxymethacrylate),methylenedibisacrylamide, vinyl esters (e.g., vinyl acetate, vinylpropionate and vinyl laurate), acrylonitrile, methacrylonitrile,aromatic vinyl compounds (e.g., styrene and its derivatives,vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene),itaconic acid, citraconic acid, crotonic acid, vinylidene chloride,vinyl alkyl ethers (e.g., vinyl ethyl ether), maleic acid, maleicanhydride, maleic esters, N-vinyl-2-pyrrolidone, N-vinylpyridine and 2-and 4-vinylpyridine, etc. Two or more of these non-color-formingethylenically unsaturated monomers described above may be used incombination.

Examples of and processes for the synthesis of couplers represented bythe above general formula (III) or (IV) are described in the literature:e.g., compounds of the general formula (III) are described in JapanesePatent Application (OPI) No. 162548/84 (corresponding to U.S. Pat. No.4,500,630) (the term "OPI" as used herein refers to a "publishedunexamined Japanese patent application"), and compounds of the generalformula (IV) in Japanese Patent Application (OPI) No. 171956/84(corresponding to European Patent No. 119,860A) and U.S. PatentApplication Ser. No. 713,989 (filed on Mar. 20, 1985). U.S. Pat. Nos.3,061,432 and 3,725,067 disclose both compounds of the general formulae(III) and (IV).

Specific examples of couplers represented by the general formula (III)or (IV) are illustrated below. However, the present invention is not tobe construed as being limited at all to the couplers set forth below.##STR9##

The reason for limiting the total number of carbon atoms of thesubstituents represented by R³, R⁴ and R⁵ in the general formula (II) to12 to 60 is that the improved effects of the present invention arereduced when the total is outside this range. In addition, if the totalnumber of carbon atoms exceeds 60, the solubility of coupler is soreduced that, in some cases, the coupler forms a precipitate, thus thetotal number of carbon atoms of more than 60 is not preferable.

In the general formula (II), the alkyl group represented by R³, R⁴ or R⁵may be either a straight chain alkyl group or a branched chain alkylgroup, such as a methyl group, an ethyl group, a propyl group, a butylgroup, a pentyl group, a hexyl group, a heptyl group, an octyl group, anonyl group, a decyl group, a undecyl group, a dodecyl group, a tridecylgroup, a tetradecyl group, a pentadecyl group, a hexadecyl group, aheptadecyl group, an octadecyl group, a nonadecyl group, an eicosylgroup, etc., and the cycloalkyl group represented by R³, R⁴ or R⁵ canbe, for example, a cyclopentyl group and a cyclohexyl group. The arylgroup represented by R³, R⁴ or R⁵ can be a phenyl group, a naphthylgroup, etc., the alkenyl group represented by R³, R⁴ or R⁵ can be abutenyl group, a pentenyl group, a hexenyl group, a heptenyl group, anoctenyl group, a decenyl group, a dodecenyl group, an octadecenyl group,etc. These alkyl, cycloalkyl, aryl and alkenyl groups may also have oneor more substituents. Examples of suitable substituents for the alkyl,cycloalkyl and alkenyl groups include a halogen atom (e.g., a fluorineatom, a chlorine atom, etc.), an alkoxy group (e.g., a methoxy group, anethoxy group, a butoxy group, etc.), an aryl group (e.g., a phenylgroup, a tolyl group, a naphthyl group, etc.), an aryloxy group (e.g., aphenoxy group, etc.), an alkenyl group, an alkoxycarbonyl group, etc.,and examples of substituents for the aryl group include an alkyl group,etc., in addition to those for the alkyl, cycloalkyl and alkenyl groupdescribed above. Preferable examples of R³, R⁴ and R⁵ include a tolylgroup, a 2-ethylhexyl group, a 7-methyloctyl group, a cyclohexyl group,a straight chain alkyl group containing 8 to 18 carbon atoms, etc.

In the present invention, the term "high boiling organic solvents" meansthose organic solvents which have a boiling point of about 175° C. orabove at atmospheric pressure.

In the present invention, the high boiling organic solvent representedby the general formula (II) may be used in any amount depending upon thekind and the amount of magenta coupler represented by the generalformula (I). However, the ratio of the high boiling organic solvent tomagenta coupler is preferably about 0.05:1 to about 20:1 by weight. Inaddition, the high boiling organic solvent to be used in the presentinvention represented by the general formula (II) may be used incombination with other conventionally known high boiling organicsolvents as long as the objects of the present invention can beachieved. Examples of such known solvents include phthalate typesolvents (e.g., dibutyl phthalate, di-2-ethylhexyl phthalate, etc.),amide type solvents (e.g., N,N-diethyldodecanamide), fatty acid estertype solvents, benzoate type solvents, phenolic solvents (e.g.,2,5-di-tert-amylphenol, etc.), etc.

Examples of processes for the synthesis of high boiling organic solventsrepresented by the general formula (II) are described in U.S. Pat. No.3,676,137, Japanese Patent Application (OPI) Nos. 119235/79, 119921/79,119922/79, 25057/80, etc.

Specific examples of high boilinr organic solvents represented by thegeneral formula (II) are illustrated below. However, the presentinvention is not to be construed to be limited thereto. ##STR10##

Dyes derived from a coupler must have a preferable hue for colorreproduction. Specifically, the color region of the main absorption isin a suitable range, and a distinct color dye with less unnecessaryabsorption is desirable. The pattern of the absorption spectrum of thedye on, particularly, the longer wavelength side greatly influences thedistinctness of color. The smaller the difference between the wavelengthat which the absorption is 50%, 10% or 2% of the maximum absorption andthe wavelength at which the absorption is maximal, the sharper the hue.Dyes with such sharp hue provide a distinct color dye with less colorstain not only when used alone but when used together with other dyeswith different hues. In the present invention, the phrase "toe cut ofabsorption" can be expressed quantitatively in terms of theabove-described 10% or 2% absorption wavelength width, etc.

The magenta couplers and the high boiling organic solvents in accordancewith the present invention can be dispersed and incorporated into atleast one hydrophilic organic colloidal layer constituting aphotographic light-sensitive layer.

Techniques for introducing couplers into a silver halide emulsion layerare known and are described in, for example, U.S. Pat. No. 2,322,027,these being generally employed.

The high boiling organic solvents represented by the general formula(II) (phosphoric ester type coupler solvents) generally have anextremely good solubility for the couplers of the present invention.However, where the solubility of the coupler is insufficient because asmall coupler solvent/coupler ratio is employed, other coupler solventssuch as phthalic ester type coupler solvents, low boiling organicsolvents, etc., may be used in combination. In the present invention, alow boiling organic solvent having a boiling point of about 30° to about150° C., such as a lower alkyl acetate (e.g., ethyl acetate, butylacetate, etc.), ethyl propionate, sec-butyl alcohol, methyl isobutylketone, β-ethoxyethyl acetate, methyl Cellosolve acetate, etc., may beallowed to coexist in the phosphoric ester type coupler solvent beforedissolving the coupler in the coupler solvent. In addition, the couplerof the present invention may be dissolved in the low boiling organicsolvent described above, then the high boiling organic solventrepresented by the general formula (II) may be added thereto.

The mixing ratio of other coupler solvents to the high boiling organicsolvents represented by the general formula (II) is in the range ofabout 0.1 to 10, preferably about 0.2 to 5 by weight.

In incorporating the coupler, thus dissolved in the coupler solventaccording to these techniques, into a silver halide emulsion layer, thedispersing technique using a polymer described in, for example, JapanesePatent Publication No. 39853/76 and Japanese Patent Application (OPI)No. 59943/76 may be employed in combination.

Where couplers have an acid group such as a carboxylic acid group or asulfonic acid group, they may be introduced into the hydrophilic colloidlayer as an alkaline aqueous solution.

As a binder or protective colloid which can be used for emulsion layersor interlayers of the light-sensitive material of the present invention,gelatin is advantageously used. However, other hydrophilic colloids maybe used alone or in combination with gelatin.

As the gelatin which can be used in the present invention, eitherlime-processed gelatin or acid-processed gelatin may be used. Detaileddescriptions on preparation of gelatin are given in Arser Wais, TheMacromolecular Chemistry of Gelatin, Academic Press (1964).

In a photographic emulsion layer of photographic light-sensitivematerial used in the present invention, any of silver bromide, silverbromoiodide, silver chlorobromoiodide, silver chlorobromide, and silverchloride may be used as the silver halide. A preferred silver halide issilver bromoiodide containing 15 mol% or less silver iodide,particularly 2 mol% to 12 mol% silver iodide.

The silver halide grains in the photographic emulsion are notparticularly limited as to mean particle size (particle diameter withrespect to spherical or approximately spherical particles, and edgelength with cubic particles; presented in terms of an average based onprojected area), with particle size of about 3 μm or less beingpreferable. The particle size distribution can be either narrow orbroad.

Silver halide grains in the photographic emulsion may be in a regularcrystal form such as a cubic or octahedral form, in an irregular crystalform such as a spherical or platy form, or in a mixed form thereof, ormay comprise a mixture of grains in different forms.

In addition, an emulsion in which superplaty silver halide grains havinga diameter-to-thickness ratio of about 5:1 or more account for 50% ormore of the total projected area may also be used.

The silver halide grains may have an inner portion and a surfafe layerdifferent from each other in phase composition. In addition, silverhalide grains of the type forming latent images mainly on the surfacethereof and grains of the type forming latent images mainly within themmay be used.

The photographic emulsion which can be used in the present invention canbe prepared by the processes described in P. Glafkides, Chimie etPhysique Photographique, Paul Montel (1967), G. F. Duffin, PhotographicEmulsion Chemistry, The Focal Press (1966), V. L. Zelikman et al.,Making and Coating Photographic Emulsions, The Focal Press (1964), etc.That is, any of an acidic process, a neutral process, and an ammoniacalprocess can be used. As a manner of reacting a soluble silver salt witha soluble halide salt, any of the single jet mixing method, double jetmixing method and a combination thereof may be employed.

A process of forming grains in the presence of excess silver ion (theso-called reversal mixing process) can be employed as well. As one typeof the double jet mixing method, a process called a controlled doublejet process wherein the pAg in the liquid phase in which the silverhalide is formed is kept constant can be employed. This process providesa silver halide emulsion containing silver halide grains of a regularcrystal form having an approximately uniform particle size.

Two or more silver halide emulsions separately prepared may be mixed foruse.

During formation or physical ripening of the silver halide grains,cadmium salts, zinc salts, lead salts, thallium salts, iridium salts orthe complex salts thereof, rhodium salts or the complex salts thereof,iron salts or the complex salts thereof, etc., may also be present.

Silver halide emulsions are usually subjected to chemical sensitization.This chemical sensitization can be conducted according to the processesdescribed in, for example, H. Frieser, Die Grundlagen derPhotographischen Prozesse mit Silberhalogeniden, AkademischeVerlagsgesellschaft (1968), pp. 675-734.

That is, sulfur sensitization using active gelatin or sulfur-containingcompounds capable of reacting with silver (e.g., thiosulfates,thioureas, mercapto compounds, rhodanines, etc.); reductionsensitization using a reductive substance (e.g., stannous salts, amines,hydrazine derivatives, formamidinesulfinic acid, silane compounds,etc.); and noble metal sensitization using compounds of noble metals(e.g., complex salts of the Group VIII metals such as Pt, Ir, Pd, etc.,as well as gold complex salts) can be employed alone or in combination.

Various compounds for the purpose of preventing formation of fog orstabilizing photographic properties may be incorporated in thephotographic emulsion used in the present invention during the steps ofproducing, or during storage or processing of, light-sensitivematerials. That is, many compounds known as antifoggants or stabilizerssuch as azoles (e.g., benzothiazolium salts, nitroimidazoles,nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles,mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles,mercaptothiadiazoles, aminotriazoles, benzotriazoles,nitrobenzotriazoles, mercaptotetrazoles (particularly1-phenyl-5-mercaptotetrazole), etc.); mercaptopyrimidines;mercaptotriazines; thioketo compounds such as oxazolinethione;azaindenes (e.g., triazaindenes, tetraazaindenes (particularly4-hydroxy-substituted (1,3,3a,7)tetraazaindenes), pentaazaindenes,etc.); benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonicacid amide, etc., can be added.

The photographic light-sensitive material of the present invention maycontain in its photographic emulsion layers or other hydrophiliccolloidal layers various surfactants for various purposes such asimprovement of coating properties, antistatic properties, slippingproperties, emulsion dispersibility, antiadhesion properties, andphotographic properties (for example, development acceleration,realization of contrasty tone, sensitization, etc.).

The light-sensitive material of the present invention may contain apolyalkylene oxide or its ether, ester or amine derivative, a thioethercompound, a thiomorpholine, a quaternary ammonium salt compound, aurethane derivative, a urea derivative, an imidazole derivative, a3-pyrazolidone, etc., for the purpose of enhancing sensitivity orcontrast or for accelerating development.

The photographic light-sensitive material of the present invention maycontain in its photographic emulsion layer or other hydrophiliccolloidal layer a dispersion of a water-insoluble or slightlywater-soluble synthetic polymer for improving dimensional stability,etc.

Photographic emulsions used in the present invention may be spectrallysensitized with methine dyes or the like. Dyes which can be used includecyanine dyes, merocyanine dyes, complex cyanine dyes, complexmerocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyesand hemioxonol dyes. Particularly useful dyes are cyanine dyes,merocyanine dyes and complex merocyanine dyes. In these dyes, any nucleiordinarily used as basic hetero ring nuclei in cyanine dyes can bepresent. That is, a pyrroline nucleus, an oxazoline nucleus, athiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazolenucleus, a selenazole nucleus, an imidazole nucleus, a tetrazolenucleus, a pyridine nucleus, etc.; those in which these nuclei are fusedwith an alicyclic hydrocarbon ring and those in which these nuclei arefused with an aromatic hydrocarbon ring, i.e., an indolenine nucleus, abenzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, anaphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazolenucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinolinenucleus, etc., can be used. These nuclei may be substituted withsubstituents at the nucleus carbon atoms.

In the merocyanine dyes or complex merocyanine dyes, 5- or 6-memberedhetero ring nuclei such as a pyrazolin-5-one nucleus, a thiohydantoinnucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dionenucleus, a rhodanine nucleus, a thiobarbituric acid nucleus, etc., maybe used as ketomethylene structure-containing nuclei.

These sensitizing dyes may be used alone or in combination.

A combination of sensitizing dyes is often employed particularly for thepurpose of supersensitization.

A dye which itself is not sensitizing or a substance which substantiallydoes not absorb visible light and which shows a supersensitizing effectmay be incorporated together with the sensitizing dye. For example,aminostilbene compounds substituted with a nitrogen-containing heteroring (for example, those described in U.S. Pat. Nos. 2,933,390 and3,635,721), aromatic organic acid-formaldehyde condensates (for example,those described in U.S. Pat. No. 3,743,510), cadmium salts, azaindenecompounds, etc., may be incorporated.

The present invention may also be applied to a multilayered, multicolorphotographic material comprising a support having thereon at least twolayers with different spectral sensitivity. Multilayered natural colorphotographic materials usually comprise a support having thereon atleast one red-sensitive emulsion layer, at least one green-sensitiveemulsion layer, and at least one blue-sensitive emulsion layer. Theorder of these layers may be optionally selected as the case demands.The red-sensitive emulsion layer usually contains a cyan dye formingcoupler, the green-sensitive emulsion layer a magenta dye formingcoupler and the blue-sensitive emulsion layer a yellow dye formingcoupler. However, in some cases, different combinations may be employed.

In the same or other photographic emulsion layer or light-insensitivelayer of the photographic light-sensitive material prepared according tothe present invention, other dye forming couplers, i.e., compoundscapable of forming color dyes by oxidative coupling with an aromaticprimary amine developing agent (e.g., a phenylenediamine derivative, anaminophenol derivative, etc.) in color development processing, may beused together with the coupler represented by the foregoing generalformula (I). For example, suitable magenta couplers include 5-pyrazolonecouplers, pyrazolobenzimidazole couplers, pyrazolo[5,1-c][1,2,4]triazolecouplers, pyrazolopyrazole couplers, pyrazolotetrazole couplers, openchain acylacetonitrile couplers, etc., suitable yellow couplers includeacylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides,etc.), etc., and suitable cyan couplers include naphthol couplers andphenol couplers. Of these couplers, non-diffusible couplers having ahydrophobic group called a ballast group or polymerized couplers areadvantageous. The couplers may be either 4-equivalent type or2-equivalent type with respect to silver ion. Colored couplers having acolor correcting effect or couplers capable of releasing a developmentinhibitor upon development (called DIR couplers) may also beincorporated. In addition to the DIR couplers, non-color-forming DIRcoupling compounds capable of forming a colorless coupling reactionproduct and releasing a development inhibitor may also be incorporated.

Two or more of the couplers of the present invention and theabove-described couplers may of course be used in one and the samelayer, or the same compound may be present in two or more differentlayers for attaining properties required for light-sensitive materials.

The photographic light-sensitive material of the present invention maycontain an organic or inorganic hardener in its photographic emulsionlayers or other hydrophilic colloidal layers. For example, chromiumsalts (e.g., chromium alum, chromium acetate, etc.), aldehydes (e.g.,formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds(e.g., dimethylolurea, methyloldimethylhydantoin, etc.), dioxanederivatives (e.g., 2,3-dihydroxydioxane, etc.), active vinyl compounds(e.g., 1,3,5-triacryloyl-hexahydro-s-triazine,1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (e.g.,2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogeic acids (e.g.,mucochloric acid, mucophenoxychloric acid, etc.), etc., can be usedalone or in combination.

Where the light-sensitive material according to the present inventioncontains a dye, an ultraviolet light absorbent, etc., in its hydrophiliccolloidal layer, they may be mordanted with a cationic polymer or thelike.

The light-sensitive material of the present invention may containhydroquinone derivatives, aminophenol derivatives, ascorbic acidderivatives, etc., as color fog preventing agents.

The light-sensitive material of the present invention may contain in itshydrophilic colloidal layer an ultraviolet light absorbent. For example,aryl groupsubstituted benzotriazole compounds (e.g., those described inU.S. Pat. No. 3,533,794), 4-thiazolidone compounds (e.g., thosedescribed in U.S. Pat. Nos. 3,314,794, 3,352,681, etc.), benzophenonecompounds (e.g., those described in Japanese Patent Application (OPI)No. 2784/71), cinnamic ester compounds (e.g., those described in U.S.Pat. Nos. 3,705,805 and 3,707,375), butadiene compounds (e.g., thosedescribed in U.S. Pat. No. 4,045,229), and benzoxidol compounds (e.g.,those described in U.S. Pat. No. 3,700,455) may be used. Ultravioletlight absorbing couplers (e.g., α-naphtholic and cyan dye formingcouplers), ultraviolet light absorbing polymers, etc., may also be used.These ultraviolet light absorbents may be mordanted in a specific layer.

The light-sensitive material of the present invention may contain awater-soluble dye as a filter dye or for various purposes such asprevention of irradiation. Examples of such dyes include oxonol dyes,hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azodyes. Oxonol dyes, hemioxonol dyes and merocyanine dyes are particularlyuseful of these dyes.

In the practice of the present invention, the following known dyestabilizers can be used in combination. Color image stabilizers used inthe present invention may be employed as a combination of two or morethereof. Suitable known dye stabilizers include, for example,hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols,p-hydroxyphenol derivatives, bisphenols, etc.

The photographic processing of the layers composed of photographicemulsion used in the present invention can be conducted by any knownprocess and using known processing solutions described in, for example,Research Disclosure, 176, pages 28 to 30.The processing temperature isusually between about 18° and about 50° C. However, temperatures lowerthan about 18° C. or higher than about 50° C. may be employed.

Suitable fixing solutions are those which have the same formulation asare ordinarily employed. Organic sulfur compounds which are known tofunction as fixing agents can be used as well as thiosulfates andthiocyanates. The fixing solution may contain a water-soluble aluminumsalt as a hardener.

Color developers generally comprise an alkaline aqueous solutioncontaining a color developing agent. Suitable color developing agentsinclude known primary aromatic amine developing agents such asphenylenediamines (e.g., 4-amino-N,N-diethylaniline,3-methyl-4-amino-N,N-diethylaniline,4-amino-N-ethyl-N-β-hydroxyethylaniline,3-methyl-4-amino-N-ethyl-N-β-hydroxyethylanilien,3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline,4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.).

In addition, those described in L. F. A. Mason, Photographic ProcessingChemistry, Focal Press (1966), pp. 226-229, U.S. Pat. Nos. 2,193,015 and2,592,364, Japanese Patent Application (OPI) No. 64933/73, etc., mayalso be used.

The color developer may further contain pH buffers such as alkali metalsulfites, carbonates, borates or phosphates, development inhibitors orantifogging agents such as bromides, iodides, and organic antifoggingagents and, if necessary, a water softener, a preservative (e.g.,hydroxylamine), an organic solvent (e.g., benzyl alcohol, diethyleneglycol, etc.), a development accelerator (e.g., polyethylene glycol, aquaternary ammonium salt, an amine, etc.), a dye forming coupler, acompetitive coupler, a fogging agent (e.g., sodium borohydride), anauxiliary developing agent (e.g., 1-phenyl-3-pyrazolidone), a viscosityimparting agent, a polycarboxylic acid type chelating agent, anantioxidant, etc.

Color developed photographic emulsion layers are usually bleached.Bleaching may be conducted separately or simultaneously with fixing.Compounds of polyvalent metals such as iron (III), cobalt (III),chromium (VI), copper (II), etc., peracids, quinones, nitroso compounds,etc., can be used as bleaching agents.

For example, ferricyanates, dichromates, organic complex salts of iron(III) or cobalt (III) such as complex salts with an aminopolycarboxylicacid (e.g., ethylenediaminetetraacetic acid, nitrilotriacetic acid,1,3-diamino-2-propanoltetraacetic acid, etc.) or an organic acid (e.g.,citric acid, tartaric acid, maleic acid, etc.); persulfates,permanganates; nitrosophenol; etc., may be used. Of these, potassiumferricyanate, iron (III) sodium ethylenediaminetetraacetate, and iron(III) ammonium ethylenediaminetetraacetate are particularly useful. Iron(III) ethylenediaminetetraacetates are useful in both an independentbleaching solution and a monobath bleach-fixing solution.

The color photographic emulsion layer in accordance with the presentinvention forming the dye image layer is coated on a flexible supportsuch as a synthetic resin film, paper or cloth usually used forphotographic light-sensitive materials. Useful flexible supports includefilms composed of semisynthetic or synthetic high polymers such ascellulose nitrate, cellulose acetate butyrate, polystyrene, polyethyleneterephthalate, polycarbonate, etc., and papers coated or liminated witha baryta layer or an α-olefin polymer (for example, polyethylene,polypropylene, etc.). The support may be colored with a dye or apigment, or may be blackened for intercepting light.

In the case of using these supports for reflection materials, a whitepigment is desirably added to the support or to a laminate layer.Suitable white pigments include titanium dioxide, barium sulfate, zincoxide, zinc sulfide, calcium carbonate, antimony trioxide, silica white,alumina white, titanium phosphate, etc. Of these, titanium dioxide,barium sulfate and zinc oxide are particularly useful.

The surface of the support is generally subbed for improving adhesion toa photographic emulsion layer or the like. The support surface may besubjected to a corona discharge treatment, a UV light irradiation, or aflame treatment before or after the subbing treatment.

In reflection materials containing the magenta couplers used in thepresent invention, polymer laminated paper is often used as support.However, the use of a synthetic resin film containing a white pigmentincorporated therein provides photographic images with particularlyexcellent saturation and expression in the dark areas as well asimproved smoothness, glossiness and sharpness, thus being particularlypreferred. In this case, polyethylene terephthalate or cellulose acetateis particularly useful as the synthetic resin material, and bariumsulfate or titanium oxide as the white pigment.

After development processing and drying, the surface and the back of thephotographic material of the present invention may be laminated withplastic film. Polyolefin, polyester, polyacrylate, polyvinyl acetate,polystyrene, butadiene-styrene copolymer, polycarbonate, etc., can beused as the laminating plastic film. Polyethylene terephthalate, vinylalcohol-ethylene copolymer, polyethylene, etc., are particularly useful.

The present invention is now illustrated in greater detail by referenceto the following examples which, however, are not to be construed aslimiting the present invention in any way. Unless otherwise indicatedall parts, percents, ratios and the like are by weight.

EXAMPLE 1

The following magenta dye obtained by reacting illustrative Coupler(M-6) with the following developing agent in the presence of ammoniumpersulfate and potassium sulfate was dissolved in an equal weight ofillustrative Compound (S-7) using ethyl acetate as assistant solvent.After evaporating off the ethyl acetate, the visible absorption spectrumof this dye solution was measured.

Developing Agent: ##STR11## Magenta Dye: ##STR12##

For comparison, the visible absorption spectrum of a dye solutionprepared by dissolving the above-described magenta dye in an equalweight of dibutyl phthalate was measured (Comparative Example 1).Further, the visible absorption spectrum of a solution prepared bydissolving the following comparative magenta dye in an equal weight ofillustrative Compound (S-7) (Comparative Example 2) and that of asolution prepared by dissolving the same dye in dibutyl phthalate(Comparative Example 3) were measured.

The thus obtained absorption spectra are shown in FIG. 1.

Comparative Magenta Dye: ##STR13##

It can be seen from FIG. 1 that, while the magenta dye formed from the5-pyrazolone type coupler does not show a great change in the absorptionspectrum when dissolved in the phosphoric ester type solvent of thepresent invention and when dissolved in dibutyl phthalate, the magentadye formed from the pyrazoloazole type coupler of the present inventionshows a greatly improved toe cut of the absorption spectrum on thelonger wavelength side when dissolved in the phosphoric ester solvent ofthe present invention in comparison with the result obtained when it isdissolved in dibutyl phthalate. In addition, since the magenta dyeformed from the pyrazoloazole type coupler used in the present inventionhas no side absorption on the shorter wavelength side, the absorptionspectrum of this magenta dye dissolved in the phosphoric ester solventof the present invention is found to be suited for improving the colorreproducibility of a color photograph. (The visual absorption spectrumwas measured using an automatic recording spectrophotometer, Model 340,made by Hitachi, Ltd.)

EXAMPLE 2

20 g of illustrative Compound (S-24) and 25 ml of ethyl acetate wereadded to 10 g of illustrative Magenta Coupler (M-6), and the resultingmixture was heated to 50° C. to prepare a solution. Then, this solutionwas added to 100 ml of an aqueous solution containing 10 g of gelatinand 1.0 g of sodium dodecylbenzenesulfonate, followed by mechanicaldispersion to prepare a fine emulsion dispersion. The total quantity ofthis emulsion dispersion was added to 100 g of a silver chlorobromideemulsion containing 50 mol% Br (containing 6.55 g of Ag), 10 ml of a 2%solution of 2,4-dihydroxy-6-chloro-s-triazine sodium salt (hardener) wasadded thereto, and the resulting mixture was coated in a silver amountof 200 mg/m² on a paper support laminated on both sides withpolyethylene, followed by providing a gelatin layer thereon to prepare asample. This sample was designated Sample A.

Then, Samples B, C and D were prepared in the same manner as describedabove except for using illustrative Compound (S-7), di-2-ethylhexylphthalate, and 2,4-di-tert-pentylphenol, respectively, in place ofillustrative Compound (S-24).

On the other hand, Sample E was prepared using the following comparativecoupler in place of Coupler (M-6) used in Example 1 and illustrativeCompound (S-24) as a solvent.

The thus prepared Samples A to E were subjected to 1,000 CMS wedgeexposure, then processed using the following solutions.

    ______________________________________                                         ##STR14##          Comparative Coupler (A)                                   ______________________________________                                        Developer:                                                                    Benzyl Alcohol           15     ml                                            Diethylenetriaminepentaacetic Acid                                                                     5      g                                             KBr                      0.4    g                                             Na.sub.2 SO.sub.3        5      g                                             Na.sub.2 CO.sub.3        30     g                                             Hydroxylamine Sulfate    2      g                                             4-Amino-3-methyl-Nβ-(methane-                                                                     4.5    g                                             sulfonamido)ethylaniline.3/2H.sub.2 SO.sub.4.H.sub.2 O                        Water to make            1,000  ml                                                                     pH:    10.1                                          Bleach-Fixing Solution:                                                       Ammonium Thiosulfate (70 wt %)                                                                         150    ml                                            Na.sub.2 SO.sub.3        5      g                                             Na[Fe(EDTA)]             40     g                                             EDTA*                    4      g                                             Water to make            1,000  ml                                                                     pH:    6.8                                           ______________________________________                                        Processing Steps                                                                              Temperature  Time                                             ______________________________________                                        Developer       33° C.                                                                              3 min 30 sec                                     Bleach Fixing Solution                                                                        33°  C.                                                                             1 min 30 sec                                     Washing with water                                                                            28-35° C.                                                                           3 min                                            ______________________________________                                         *EDTA means ethylenediaminetetraacetic acid                              

The reflection spectrum of each of the thus obtained dye images of thesamples was measured at a εmax of 1.0 using an automatic recordingspectrophotometer, Model 340 (made by Hitachi, Ltd.), to obtain theresults shown in FIG. 2 (with the reference of magnesium oxide).

As a result, it is seen that the high boiling phosphoric ester solventof the present invention represented by the general formula (II) givesthe pyrazoloazole type coupler of the present invention desirablespectral absorption characteristics as magenta color forming agent forsubtractive color photography, i.e., less absorption on the longerwavelength side (600 nm and longer), no side absorption as is differentfrom known pyrazolone type couplers, and less absorption on the shorterwavelength side, thus giving preferred spectral absorption curve forcolor reproduction.

EXAMPLE 3

A first layer (lowermost layer) to a seventh layer (uppermost layer)were coated as shown in Table I below on a paper laminated withpolyethylene on both sides to prepare Color Photographic Light-SensitiveMaterials F to J.

The coating solutions for forming the respective emulsion layers wereprepared according to the procedures described in Example 2.

In Samples F, G, H and I, Coupler (M-6) is used as a magenta coupler andCompound (S-24) for Sample F, Compound (S-7) for Sample G,di-2-ethylhexyl phthalate for Sample H and 2,4-di-tert-pentylphenol forSample I are used as a solvent in the 3rd layer. In Sample J,Comparative Coupler (A) is used as a magenta coupler and Compound (S-24)is used as a solvent in the 3rd layer.

Each of these five (F to J) samples was exposed using a B-G-R threecolor separation filter, and processed in the same manner as describedin Example 2.

Of the thus obtained samples, Samples F and G provided distinct imageshaving high saturation. However, Samples H, I and J provided imageshaving low saturation, and Samples H and I gave violet tone, which isdisadvantageous with respect to color reproduction.

                  TABLE I                                                         ______________________________________                                        7th Layer                                                                             Gelatin (coated amount: 1,600 mg/m.sup.2)                             6th Layer                                                                             Gelatin (coated amount: 1,000 mg/m.sup.2)                                     UV Light Absorbent *1 (coated amount: 360 mg/m.sup.2)                         Solvent *2 (coated amount: 120 mg/m.sup.2)                            5th Layer                                                                             AgClBr Emulsion (Br: 50 mol %; coated silver                                  amount: 300 mg/m.sup.2)                                                       Gelatin (coated amount: 1,200 mg/m.sup.2)                                     Cyan Coupler *3 (coated amount: 400 mg/m.sup.2)                               Solvent *2 (coated amount: 250 mg/m.sup.2)                            4th Layer                                                                             Gelatin (coated amount: 1,600 mg/m.sup.2)                                     UV Light Absorbent *1 (coated amount: 700 mg/m.sup.2)                         Color Stain Preventing Agent *4 (coated                                       amount: 200 mg/m.sup.2)                                                       Solvent *2 (coated amount: 300 mg/m.sup.2)                            3rd Layer                                                                             AgClBr Emulsion (Br: 50 mol %; coated silver                                  amount: 180 mg/m.sup.2)                                                       Magenta Coupler *5 (coated amount: 275 mg/m.sup.2)                            Solvent *6 (coated amount: 550 mg/m.sup.2)                            2nd Layer                                                                             Gelatin (coated amount: 1,100 mg/m.sup.2)                                     Color Stain Preventing Agent *4 (coated                                       amount: 200 mg/m.sup.2)                                                       Solvent *2 (coated amount: 100 mg/m.sup.2)                            1st Layer                                                                             AgClBr Emulsion (Br: 80 mol %; coated silver                                  amount 350 mg/m.sup.2)                                                        Gelatin (coated amount: 1,500 mg/m.sup.2)                                     Yellow Coupler *7 (coated amount: 500 mg/m.sup.2)                             Solvent *8 (coated amount: 400 mg/m.sup.2)                            Support Paper support laminated with polyethylene on                                  both sides                                                            ______________________________________                                         *1 UV Light Absorbent:                                                        2(2-Hydroxy-3-sec-butyl-5-tert-butylphenyl)benzotriazole                      *2 Solvent: Dibutyl phthalate                                                 *3 Cyan Coupler:                                                              2[α-(2,4-Di-tert-pentylphenoxy)-butanamido]-4,6-dichloro-5-methylph    nol                                                                            *4 Color Stain Preventing Agent: 2,5Dioctylhydroquinone                       *5 Magenta Coupler: (M6) and Comparative Coupler (A)                          *6 Solvent: (S24), (S7), di2-ethylhexyl phthalate, 2,4di-tert-pentylpheno     *7 Yellow Coupler:                                                            α-Pivaloylα-(2,4-dioxo-5,5'-dimethyloxazolidin-3-yl)-2-chloro    5-[α-(2,4-di-tert-pentylphenoxy)butanamido]-acetanilide                  *8 Solvent: Dioctylbutyl phosphate                                       

EXAMPLE 4

Samples F to J prepared in Example 3 were exposed in the same manner asdescribed in Example 2 using a B-G-R three color separation filter, andprocessed in the same manner. The thus obtained samples were subjectedto three week fading test using a fluorescent lamp fading apparatus(15,000 lux). The results thus obtained are shown in Table II below.

                  TABLE II                                                        ______________________________________                                                             Change in Matenta Density                                Sample   Solvent     (initial density = 1.0)                                  ______________________________________                                        F        (S-24)      0.75                                                     G        (S-7)       0.78                                                     H        Di-2-ethylhexyl                                                                           0.63                                                              phthalate                                                            I        2,4-Di-tert-                                                                              0.57                                                              pentylphenol                                                         J        (S-24)      0.69                                                     ______________________________________                                    

It can be seen from the above results that the use of the high boilingsolvent represented by the general formula (II) for the pyrazoloazoletype compound used in the present invention is also effective forimproving color image fastness.

EXAMPLE 5

A multilayered color light-sensitive material comprising a cellulosetriacetate film support having provided thereon in sequence the layershaving the following formulations was prepared.

    ______________________________________                                        1st Layer: Antihalation Layer                                                 Black colloidal silver                                                                            0.2       g of Ag/m.sup.2                                 Gelatin             1.5       g/m.sup.2                                       UV-1 (UV ray absorbent)                                                                           0.1       g/m.sup.2                                       UV-2 (UV ray absorbent)                                                                           0.2       g/m.sup.2                                       Oil-1 (oil for dispersing UV-1                                                                    0.01      g/m.sup.2                                       and UV-2)                                                                     Oil-2 (oil for dispersing UV-1                                                                    0.01      g/m.sup.2                                       and UV-2)                                                                     2nd Layer: Interlayer                                                         Fine grained silver halide (AgBr                                                                  0.15      g of Ag/m.sup.2                                 of 0.07 μm in mean grain size)                                             Gelatin             1.0       g/m.sup.2                                       Cpd-6 (coupler)     0.1       g/m.sup.2                                       Cpd-5 (coupler)     0.02      g/m.sup.2                                       Oil-1 (oil for dispersing Cpd-5 and 6)                                                            0.1       g/m.sup.2                                       3rd Layer:                                                                    First Red-Sensitive Emulsion Layer                                            Silver bromoiodide emulsion                                                                       0.5       g of Ag/m.sup.2                                 (mean grain size: 0.7 μm;                                                  distribution of iodide: uniform                                               within grains; AgI: 3 mol %)                                                  Silver bromoiodide emulsion                                                                       0.2       g of Ag/m.sup.2                                 (mean grain size: 0.3 μm;                                                  distribution of iodide: uniform                                               within grains; AgI: 3 mol %)                                                  Gelatin             2.5       g/m.sup.2                                       P-1 (sensitizing dye)                                                                             4.5 × 10.sup.-4                                                                   mol/mol Ag                                      P-2 (sensitizing dye)                                                                             1.5 × 10.sup.-4                                                                   mol/mol Ag                                      Cpd-5 (coupler)     0.5       g/m.sup.2                                       Cpd-1 (DIR coupler) 0.02      g/m.sup.2                                       Cpd-5 (coupler)     0.22      g/m.sup. 2                                      Oil-1 (oil for dispersing Cpd-1 and 5)                                                            0.3       g/m.sup.2                                       Oil-2 (oil for dispersing Cpd-1 and 5)                                                            0.3       g/m.sup.2                                       4th Layer: Second                                                             Red-Sensitive Emulsion Layer                                                  Silver bromoiodide emulsion                                                                       1.2       g of Ag/m.sup.2                                 (mean grain size: 1.0 μm;                                                  iodide distribution: non-uniform                                              within and between grains;                                                    prepared by single jet process;                                               silver iodide: 10 mol %)                                                      Gelatin             1.5       g/m.sup.2                                       P-1 (sensitizing dye)                                                                             3 × 10.sup.-4                                                                     mol/mol Ag                                      P-2 (sensitizing dye)                                                                             1 × 10.sup.-4                                                                     mol/mol Ag                                      Cpd-5 (coupler)     0.28      g/m.sup.2                                       Oil-1 (oil for dispersing Cpd-5)                                                                  0.12      g/m.sup.2                                       Oil-2 (oil for dispersing Cpd-5)                                                                  0.12      g/m.sup.2                                       5th Layer:                                                                    Third Red-Sensitive Emulsion Layer                                            Silver bromoiodide emulsion                                                                       2         g/m.sup.2                                       (mean grain size: 2.0 μm;                                                  spherical grains prepared by                                                  using ammonia upon formation                                                  of grains; AgI: 7 mol %)                                                      Gelatin             2         g/m.sup.2                                       P-1 (sensitizing dye)                                                                             2 × 10.sup.-4                                                                     mol/mol Ag                                      P-2 (sensitizing dye)                                                                             0.6 × 10.sup.-4                                                                   mol/mol Ag                                      Cpd-5 (coupler)     0.28      g/m.sup.2                                       Oil-1 (oil for dispersing Cpd-5)                                                                  0.12      g/m.sup.2                                       Oil-2 (oil for dispersing Cpd 5)                                                                  0.12      g/m.sup.2                                       6th Layer: Interlayer                                                         Gelatin             1.0       g/m.sup.2                                       Cpd-2 (for preventing color mixing)                                                               0.2       g/m.sup.2                                       Oil-1 (oil for dispersing Cpd-2)                                                                  0.1       g/m.sup.2                                       Oil-2 (oil for dispersing Cpd-2)                                                                  0.1       g/m.sup.2                                       7th Layer: First                                                              Green-Sensitive Emulsion Layer                                                Silver bromoiodide emulsion                                                                       0.3       g/m.sup.2                                       (mean grain size: 0.7 μm;                                                  iodide distribution: uniform                                                  within grains; AgI: 3 mol %)                                                  Silver bromoiodide emulsion                                                                       0.1       g/m.sup.2                                       (mean grain size: 0.3 μm;                                                  iodide distribution: uniform                                                  within grains; AgI: 3 mol %)                                                  Gelatin             0.8       g/m.sup.2                                       O-1 (sensitizing dye)                                                                             5 × 10.sup.-4                                                                     mol/mol Ag                                      O-2 (sensitizing dye)                                                                             2 × 10.sup.-4                                                                     mol/mol Ag                                      Cpd-6 (coupler)     0.36      g/m.sup.2                                       Cpd-3 (DIR coupler) 0.06      g/m.sup.2                                       Oil-1 (oil for dispersing Cpd-3 and 6)                                                            0.2       g/m.sup.2                                       8th Layer: Second                                                             Green-Sensitive Emulsion Layer                                                Silver bromoiodide emulsion                                                                       1         g of Ag/m.sup.2                                 (mean grain size: 1.0 μm;                                                  iodide distribution: non-uniform                                              within and between grains;                                                    prepared by single jet process;                                               AgI: 10 mol %)                                                                Gelatin             1         g/m.sup.2                                       O-1 (sensitizing dye)                                                                             3.5 × 10.sup.-4                                                                   mol/mol Ag                                      O-2 (sensitizing dye)                                                                             1.4 × 10.sup.-4                                                                   mol/mol Ag                                      Cpd-6 (coupler)     0.30      g/m.sup.2                                       Oil-1 (oil for dispersing Cpd-6)                                                                  0.15      g/m.sup.2                                       9th Layer: Third                                                              Green-Sensitive Emulsion Layer                                                Silver bromoiodide emulsion                                                                       2         g/m.sup.2                                       (mean grain size: 2.0 μm;                                                  spherical grains prepared by                                                  using ammonia upon formation                                                  of grains; AgI: 7 mol %)                                                      Gelatin             2         g/m.sup.2                                       O-1 (sensitizing dye)                                                                             2 × 10.sup.-4                                                                     mol/mol Ag                                      O-2 (sensitizing dye)                                                                             0.8 × 10.sup.-4                                                                   mol/mol Ag                                      Cpd-6 (coupler)     0.18      g/m.sup.2                                       Oil-1 (oil for dispersing Cpd-6)                                                                  0.2       g/m.sup.2                                       10th Layer: Yellow Filter Layer                                               Yellow colloidal silver                                                                           0.04      g of Ag/m.sup.2                                 Gelatin             1         g/m.sup.2                                       Cpd-2 (agent for preventing                                                                       0.2       g/m.sup.2                                       color mixing)                                                                 Oil-1 (oil for dispersing Cpd-2)                                                                  0.1       g/m.sup.2                                       Oil-2 (oil for dispersing Cpd-2)                                                                  0.1       g/m.sup.2                                       11th Layer:                                                                   First Blue-Sensitive Emulsion Layer                                           Silver bromoiodide emulsion                                                                       0.2       g/m.sup.2                                       (mean grain size: 0.7 μm;                                                  iodide distribution: uniform                                                  within grains; AgI: 3 mol %)                                                  Silver bromoiodide emulsion                                                                       0.7       g/m.sup.2                                       (mean grain size: 0.3 μm;                                                  distribution of iodide: uniform                                               within grains; AgI: 3 mol %)                                                  Gelatin             1.2       g/m.sup.2                                       O-3 (sensitizing dye)                                                                             3 × 10.sup.-4                                                                     mol/mol Ag                                      Cpd-4 (coupler)     0.7       g/m.sup.2                                       Cpd-3 (DIR coupler) 0.03      g/m.sup.2                                       Oil-1 (oil for dispersing Cpd-3 and 4)                                                            0.5       g/m.sup.2                                       12th Layer: Second                                                            Blue-Sensitive Emulsion Layer                                                 Silver bromoiodide emulsion                                                                       0.3       g of Ag/m.sup.2                                 (mean grain size: 1.0 μm;                                                  iodide distribution: non-uniform                                              within and between grains;                                                    prepared by single jet process;                                               AgI: 10 mol %)                                                                Gelatin             0.4       g/m.sup.2                                       O-3                 2 × 10.sup.-4                                                                     mol/mol Ag                                      Cpd-4 (coupler)     0.3       g/m.sup.2                                       Oil-1 (oil for dispersing Cpd-4)                                                                  0.2       g/m.sup.2                                       13th Layer:                                                                   Third Blue-Sensitive Emulsion Layer                                           Silver bromoiodide emulsion                                                                       1         g of Ag/m.sup.2                                 (mean grain size: 2.0 μm;                                                  spherical grains prepared by                                                  using ammonia upon formation                                                  of grains; AgI: 7 mol %)                                                      Gelatin             0.7       g/m.sup.2                                       O-3 (sensitizing dye)                                                                             1.5 × 10.sup.-4                                                                   mol/mol Ag                                      Cpd-4 (coupler)     0.2       g/m.sup.2                                       Oil-1 (oil for dispersing Cpd-4)                                                                  0.14      g/m.sup.2                                       14th Layer: First Protective Layer                                            Gelatin             1.5       g/m.sup.2                                       UV-1 (UV light absorbent)                                                                         0.1       g/m.sup.2                                       UV-2 (UV Light absorbent)                                                                         0.2       g/m.sup.2                                       Oil-1 (oil for dispersing UV-1 and 2)                                                             0.01      g/m.sup.2                                       Oil-2 (oil for dispersing UV-1 and 2)                                                             0.01      g/m.sup.2                                       15th Layer: Second Protective Layer                                           Fine grained silver halide                                                                        0.5       g of Ag/m.sup.2                                 (AgBr; mean grain size: 0.07 μm)                                           Gelatin             1         g/m.sup.2                                       Polymethyl methacrylate                                                                           0.2       g/m.sup.2                                       particles (diameter: about 1.5 μm)                                         W-1 (static electrification                                                                       0.02      g/m.sup.2                                       controlling agent)                                                            H-1 (hardener)      0.4       g/m.sup.2                                       S-1 (formaldehyde scavenger)                                                                      1         g/m.sup.2                                       ______________________________________                                    

The thus obtained sample was subjected to gradation exposure using a4,800° K. white light, then to the following development processing,followed by sensitometry using a densitometer fitted with a status Mfilter.

The development processing was conducted at 38° C. as follows.

    ______________________________________                                        1. Color Development 3 min & 15 sec                                           2. Bleaching         6 min & 30 sec                                           3. Washing with Water                                                                              3 min & 15 sec                                           4. Fixing            6 min & 30 sec                                           5. Washing with Water                                                                              3 min & 15 sec                                           6. Stabilizing       3 min & 15 sec                                           ______________________________________                                    

Formulations of the processing solutions used in respective steps are asfollows.

    ______________________________________                                        Color Developer:                                                              Sodium Nitrilotriacetate 1.0    g                                             Sodium Sulfite           4.0    g                                             Sodium Carbonate         30.0   g                                             Potassium Bromide        1.4    g                                             Hydroxylamine Sulfate    2.4    g                                             4-(N--Ethyl-N--β-hydroxyethylamino)-2-                                                            4.5    g                                             methylaniline Sulfate                                                         Water to make            1      liter                                         Bleaching Solution:                                                           Ammonium Bromide         160.0  g                                             Aqueous Ammonia (28%)    25.0   cc                                            Sodium Iron Ethylenediaminetetraacetate                                                                130.0  g                                             Glacial Acetic Acid      14.0   cc                                            Water to make            1      liter                                         Fixing Solution:                                                              Sodium Tetrapolyphosphate                                                                              2.0    g                                             Sodium Sulfite           4.0    g                                             Ammonium Thiosulfate (70%)                                                                             175.0  cc                                            Sodium Bisulfite         4.6    g                                             Water to make            1      liter                                         Stabilizing Solution:                                                         Formalin                 8.0    cc                                            Water to make            1      liter                                         ______________________________________                                    

Chemical structures of the compounds used in Example 5 are illustratedbelow. ##STR15##

EXAMPLE 6

Onto a triacetate film base were coated, in this order, the followinglayers.

1st Layer: Antihalation Layer

A layer of gelatin containing black colloidal silver.

2nd Layer: Gelatin Interlayer

3rd Layer: Slow Speed Red-Sensitive Emulsion Layer

A layer of gold and sulfur sensitized slow speed silver iodobromideemulsion having a silver iodide content of 3.6 mol % and an averagegrain size of about 0.3 μm and incorporated with a sensitizing dye:

3,3'-di(3-sulfopropyl)-9-ethylnaphtho[1,2-d]carbocyanine

and a cyan coupler emulsion consisting of:

2-(heptafluorobutanoylamido)-5-[2'-(2",4"-di-t-amylphenoxy)butanoylamido]phenol(coupler); and tricresyl phosphate (coupler solvent).

This layer had a silver/coupler ratio of 17.0 and a silver coverage of0.9 g/m².

4th Layer: High Speed Red-Sensitive Emulsion Layer

A layer of gold and sulfur sensitized high speed silver iodobromideemulsion having a silver iodide content of 3.5 mol % and an averagegrain size of about 0.6 μm and incorporated with the same sensitizingdye and cyan coupler emulsion as in the 3rd Layer.

This layer had a silver coverage of 0.4 g/m².

5th Layer: Gelatin Interlayer

6th Layer: Interlayer

A layer of prefogged silver bromide emulsion containing grains with fogson the surface thereof and having an average grain size of about 0.15μm. This layer had a silver coverage of 0.03 g/m² and a gelatin coverageof 0.4 g/m².

7th Layer: Slow Speed Green-Sensitive Emulsion Layer

A layer of gold and sulfur sensitized slow speed silver iodobromideemulsion having a silver iodide content of 3 mol % and an average grainsize of about 0.3 μm and incorporated with a sensitizing dye:

sodium salt of5,5'-diphenyl-9-ethyl-3,3'-disulfoethylbenzoxacarbocyanine

and a magenta coupler emulsion consisting of: ##STR16## andtri(2-ethylhexyl) phosphate (coupler solvent). This layer had asilver/coupler ratio of 15.0 and a silver coverage of 0.50 g/m².

8th Layer: High Speed Green-Sensitive Emulsion Layer

A layer of gold and sulfur sensitized high speed silver iodobromideemulsion having a silver iodide content of 2.6 mol % and an averagegrain size of about 0.9 μm and incorporated with the same sensitizingdye and magenta coupler emulsion as in the 7th layer described above.

This layer had a silver coverage of 0.30 g/m².

9th Layer: Gelatin Interlayer

10th Layer: Yellow Filter Layer

A layer of gelatin containing yellow colloidal silver.

11th Layer: Slow Speed Blue-Sensitive Emulsion Layer

A layer of gold and sulfur sensitized silver iodobromide emulsion havinga silver iodide content of 4 mol % and an average grain size of about0.4 μm and incorporated with a yellow coupler emulsion consisting of:

α-(4-pivaloyl)-α-(1-benzyl-5-ethoxy-3-hydantoinyl)-2-chloro-5-dodecyloxycarbonylacetanilide(coupler); and tricresyl phosphate (coupler solvent).

This layer had a silver/coupler ratio of 13.0 and a silver coverage of0.9 g/m².

12th Layer: High Speed Blue-Sensitive Emulsion Layer

A layer of gold and sulfur sensitized high speed silver iodobromideemulsion layer having a silver iodide content of 2.6 mol % and anaverage grain size of about 1.0 μm and incorporated with the same yellowcoupler emulsion as in 11th Layer described above.

This layer had a silver coverage of 0.6 g/m².

13th Layer: Protective Gelatin Layer

Upon coating, each of the above-mentioned layers was additionallyincorporated with:

4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene (stabilizer);1,2-bis(vinylsulfonylacetamido)ethane (hardener); sodiump-dodecylbenzenesulfonate (coating aid); and sodiump-nonylphenoxypoly(ethylenoxy)propanesulfonate (coating aid).

The thus prepared color reversal photographic light-sensitive material(control sample) is designated as Sample 1.

Then, Sample 2 was prepared in the same manner as with Sample 1 exceptfor using Coupler (M-37) of the following structure: ##STR17## forgreen-sensitive emulsion layer in place of Coupler (M-49).

Further, a control sample was prepared in absolutely the same manner aswith Sample 1 except for changing the coupler in the green-sensitiveemulsion layer to1-(2,4,6-trichlorophenyl)-3-[3-(2,5-di-tertamylphenoxyacetamido)benzamido]-5-pyrazoloneand changing the silver/coupler ratio to 30.0 and the coated silveramount to 1.0 g/m² and 0.60 g/m² (in 8th Layer). The thus preparedsample was designated as Sample 3.

Another control sample was prepared in absolutely the same manner aswith Sample 1 except for using the same coupler as that used in Sample 3and changing the coupler solvent to di(2-ethylhexyl) phthalate. The thusobtained sample was designated as Sample 4.

Samples 1 to 4 were exposed through an optical wedge fitted with a B-G-Rthree color filter and then subjected to color reversal processing inaccordance with processing prescriptions 1, 2, 3 and 4 of the following:

    ______________________________________                                        Processing Prescription 1:                                                    Processing Steps:                                                                            Time  Temperature                                                             (min) (°C.)                                             ______________________________________                                        First Development                                                                              6       38                                                   Washing          2       "                                                    Reversal         2       "                                                    Color Development                                                                              6       "                                                    Compensating     2       "                                                    Bleaching        6       "                                                    Fixing           4       "                                                    Washing          4       "                                                    Stabilizing      1       Ordinary                                                                      Temperature                                          Drying                                                                        ______________________________________                                    

For the above processing steps were used the following processingsolutions:

    ______________________________________                                        First Developer:                                                              Water                      700    ml                                          Sodium Tetrapolyphosphate  2      g                                           Sodium Sulfite             20     g                                           Hydroquinone.Monosulfonate 30     g                                           Sodium Carbonate (monohydrate)                                                                           30     g                                           1-Phenyl-4-methyl-4-hydroxymethyl-3-                                                                     2      g                                           pyrazolidone                                                                  Potassium Bromide          0.63   g                                           Potassium Thiocyanate      1.2    g                                           Potassium Iodide (0.1% solution)                                                                         2      ml                                          Water to make              1,000  ml                                          (pH was adjusted to 10.1)                                                     Reversal Solution:                                                            Water                      700    ml                                          Hexasodium Nitro-N,N,N--trimethylene                                                                     3      g                                           Phosphate                                                                     Stannous Chloride (dihydrate)                                                                            1      g                                           p-Aminophenol              0.1    g                                           Sodium Hydroxide           8      g                                           Glacial Acetic Acid        15     ml                                          Water to make              1,000  ml                                          Color Developer:                                                              Water                      700    ml                                          Sodium Tetrapolyphosphate  2      g                                           Sodium Sulfite             7      g                                           Sodium Tertiary Phosphate (12 hydrate)                                                                   36     g                                           Potassium Bromide          1      g                                           Potassium Iodide (0.1% solution)                                                                         90     ml                                          Sodium Hydroxide           3      g                                           Citrazinic Acid            15     g                                           N--Ethyl-N--(β-methanesulfonamidoethyl)-3-                                                          11     g                                           methyl-4-aminoaniline Sulfate                                                 Ethylenediamine            3      g                                           Water to make              1,000  ml                                          Compensation Solution:                                                        Water                      700    ml                                          Sodium Sulfite             12     g                                           Sodium Ethylenediaminetetraacetate                                                                       8      g                                           (2H.sub.2 O)                                                                  Thioglycerol               0.4    ml                                          Glacial Acetic Acid        3      ml                                          Water to make              1,000  ml                                          Bleaching Solution:                                                           Water                      800    ml                                          Sodium Ethylenediaminetetraacetate                                                                       2      g                                           (2H.sub.2 O)                                                                  Iron (III) Ammonium Ethylenediamine-                                                                     120    g                                           tetraacetate (2H.sub.2 O)                                                     Potassium Bromide          100    g                                           Water to make              1,000  ml                                          Fixing Solution:                                                              Water                      800    ml                                          Ammonium Thiosulfate       80     g                                           Sodium Sulfite             5      g                                           Sodium Bisulfate           5      g                                           Water to make              1,000  ml                                          Stabilizing Solution:                                                         Water                      800    ml                                          Formalin (37 wt %)         5      ml                                          Fuji Driwel                5      ml                                          Water to make              1,000  ml                                          ______________________________________                                    

Of the thus prepared samples, Samples 1 and 2 obtained by thecombination of the coupler of the present invention and the high-boilingsolvent represented by the general formula (II) of the present invention(i.e., the phosphate type oil) provided magenta color images havinghigher distinctness and higher saturation than that of the magenta colorimages provided by Control Samples 3 and 4.

The above-described advantages of the samples in accordance with thepresent invention, which are obtained by removing side absorption on theshorter wavelength side as is seen with pyrazolone couplers and reducingthe absorption on the longer wavelength (longer than 600 nm) throughcombination of the coupler and the phosphate type oil, are useful withrespect to color reproduction.

Additionally, when these samples were stored for 1 week under theconditions of 70° C. and 89% RH, the following results were obtained.

                  TABLE                                                           ______________________________________                                        Sample      70° C., 80%, 1 Week*.sup.1                                                            Stain*.sup.2                                       ______________________________________                                        1           0.99           0.06                                               2           0.98           0.06                                               3           0.85           0.24                                               4           0.78           0.33                                               ______________________________________                                         *.sup.1 Numerals represent residual densities of portions having an           initial density D.sub.G of 0.                                                 *.sup.2 D.sub.B of highlight portions after storing for 1 week at             70° C. and 80% RH.                                                

These results demonstrate that the combination of the coupler and thephosphate oil in accordance with the present invention is also excellentin preservability of formed color images, and has the merit thatacceleration of fading due to remaining coupler and generation of colorstain are not caused.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A silver halide color photographiclight-sensitive material, which comprises a support having thereon atleast one silver halide emulsion layer containing dispersed therein atleast one magenta coupler represented by the following general formula(I): ##STR18## wherein R¹ and R², which may be the same or different,each represents a hydrogen atom or a substituent, X represents ahydrogen atom or a group capable of being eliminated upon coupling withan oxidation product of an aromatic primary amine developing agent, Zrepresents a nitrogen atom or CR₆ where R₆ represents a hydrogen atom ora substituent and the magenta coupler may form a dimer or higher polymerat R¹, R², R⁶ or X;together with at least one high boiling organicsolvent represented by the following general formula (II): ##STR19##wherein R³, R⁴ and R⁵, which may be the same or different, eachrepresents an alkyl group, a cycloalkyl group, an alkenyl group or anaryl group, provided that the total number of carbon atoms in the groupsrepresented by R³, R⁴ and R⁵ is 12 to
 60. 2. The light-sensitivematerial of claim 1, wherein said coupler represented by the generalformula (I) is 1H-imidazo[1,2-b]pyrazoles or1H-pyrazolo-[1,5-b][1,2,4]triazoles.
 3. The light-sensitive material ofclaim 1, wherein said coupler represented by the general formula (I) hasthe general formula (III) or (IV): ##STR20## wherein R¹, R² and R⁶,which may be the same or different, each represents a hydrogen atom, ahalogen atom, an alkyl group, an aryl group, a heterocyclic group, acyano group, an alkoxy group, an aryloxy group, a heterocyclic oxygroup, an acyloxy group, a carbamoyloxy group, a silyloxy group, asulfonyloxy group, an acylamino group, an anilino group, a ureido group,an imido group, a sulfamoylamino group, a carbamoylamino group, analkylthio group, an arylthio group, a heterocyclic thio group, analkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamidogroup, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonylgroup, a sulfinyl group, an alkoxycarbonyl group, or an aryloxycarbonylgroup, and X represents a hydrogen atom, a halogen atom, a carboxygroup, or another coupling off group bound to the carbon atom in thecoupling position through an oxygen atom, a nitrogen atom or a sulfuratom, or R¹, R², R⁶ or X also may be a divalent group forming a bisderivative or a bond or a linking group to an ethylenically unsaturatedgroup.
 4. The light-sensitive material of claim 3, wherein R¹, R² and R⁶each represents a hydrogen atom, a chlorine atom, a bromine atom, amethyl group, a propyl group, a t-butyl group, a trifluoromethyl group,a tridecyl group, a 3-(2,4-di-t-amylphenoxy)propyl group, a2-dodecyloxyethyl group, a 3-phenoxypropyl group, a 2-hexylsulfonylethylgroup, a cyclopentyl group, a benzyl group, a phenyl group, a4-t-butylphenyl group, a 2,4-di-t-amylphenyl group, a4-tetradecanamidophenyl group, a 2-furyl group, a 2-thienyl group, a2-pyrimidinyl group, a 2-benzothiazolyl group, a cyano group, a methoxygroup, an ethoxy group, a 2-methoxyethoxy group, a 2-dodecyloxyethoxygroup, a 2-methanesulfonylethoxy group, a phenoxy group, a2-methylphenoxy group, a 4-t-butylphenoxy group, a 2-benzimidazolyloxygroup, an acetoxy group, a hexadecanoyloxy group, anN-phenylcarbamoyloxy group, an N-ethylcarbamoyloxy group, atrimethylsilyloxy group, a dodecylsulfonyloxy group, an acetamido group,a benzamido group, a tetradecanamido group, anα-(2,4-di-t-amylphenoxy)butyramido group, a γ-(3-t-butyl-4-hydroxyphenoxy)butyramido group, anα-[4-(4-hydroxyphenylsulfonyl)phenoxy]decanamido group, a phenylaminogroup, a 2-chloroanilino group, a 2-chloro-5-tetradecanamidoanilinogroup, a 2-chloro-5-dodecyloxycarbonylanilino group, an N-acetylanilinogroup, a 2-chloro-5-[α-(3-t-butyl-4-hydroxyphenoxy)dodecanamido]-anilino group, aphenylureido group, a methylureido group, an N,N-dibutylureido group, anN-succinimido group, a 3-benzylhydantoinyl group, a4-(2-ethylhexanoylamino)phthalimido group, an N,N-dipropylsulfamoylaminogroup, an N-methyl-N-decylsulfamoylamino group, a methylthio group, anoctylthio group, a tetradecylthio group, a 2-phenoxyethylthio group, a3-phenoxypropylthio group, a 3-(4-t-butylphenoxy)propylthio group, aphenylthio group, a 2-butoxy-5-t-octylphenylthio group, a3-pentadecylphenylthio group, a 2-carboxyphenylthio group, a4-tetradecanamidophenylthio group, a 2-benzothiazolylthio group, amethoxycarbonylamino group, a tetradecyloxycarbonylamino group, aphenoxycarbonylamino group, a 2,4-di-tert-butylphenoxycarbonylaminogroup, a methanesulfonamido group, a hexadecanesulfonamido group, abenzenesulfonamido group, a p-toluenesulfonamido group, anoctadecanesulfonamido group, a 2-methyloxy-5-t-butylbenzenesulfonamidogroup, an N-ethylcarbamoyl group, an N,N-dibutylcarbamoyl group, anN-(2-dodecyloxyethyl)carbamoyl group, an N-methyl-N-dodecylcarbamoylgroup, an N-[3-(2,4-di-tert-amylphenoxy)propyl]carbamoyl group, anacetyl group, a (2,4-di-tert-amylphenoxy)acetyl group, a benzoyl group,an N-ethylsulfamoyl group, an N,N-dipropylsulfamoyl group, anN-(2-dodecyloxyethyl)sulfamoyl group, an N-ethyl-N-dodecylsulfamoylgroup, an N,N-diethylsulfamoyl group, a methanesulfonyl group, anoctanesulfonyl group, a benzenesulfonyl group, a toluenesulfonyl group,an octanesulfinyl group, a dodecylsulfinyl group, a phenylsulfinylgroup, a methoxycarbonyl group, a butyloxycarbonyl group, adodecylcarbonyl group, an octadecylcarbonyl group, a phenyloxycarbonylgroup or a 3-pentadecyloxycarbonyl group, and X represents a hydrogenatom, a chlorine atom, a bromine atom, an iodine atom, a carboxyl group,an acetoxy group, a propanoyloxy group, a benzoyloxy group, a2,4-dichlorobenzoyloxy group, an ethoxyoxaloyloxy group, a pyruvinyloxygroup, a cinnamoyloxy group, a phenoxy group, a 4-cyanophenoxy group, a4-methanesulfonamidophenoxy group, a 4-methanesulfonylphenoxy group, anα-naphthoxy group, a 3-pentadecylphenoxy group, a benzyloxycarbonyloxygroup, an ethoxy group, a 2-cyanethoxy group, a benzyloxy group, a2-phenethyloxy group, a 2-phenoxyethoxy group, a 5-phenyltetrazolyloxygroup, a 2-benzothiazolyloxy group, a benzenesulfonamido group, anN-ethyltoluenesulfonamido group, a heptalfuorobutanamido group, a2,3,4,5,6-pentafluorobenzamido group, an octanesulfonamido group, ap-cyanophenylureido group, an N,N-diethylsulfamoylamino group, a1-piperidyl group, a 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl group, a1-benzylethoxy-3-hydantoinyl group, a2N-1,1-dioxo-3(2H)-oxo-1,2-benzoisothiazolyl group, a2-oxo-1,2-dihydro-1-pyridinyl group, an imidazolyl group, a pyrazolylgroup, a 3,5-diethyl-1,2,4-triazol-1-yl group, a 5- or6-bromobenzotriazol-1-yl group, a 5-methyl-1,2,3,4-triazol-1-yl group, abenzimidazolyl group, a 3-benzyl-1-hydantoinyl group, a1-benzyl-5-hexadecyloxy-3-hydantoinyl group, a 5-methyl-1-tetrazolylgroup, a 4-methoxyphenylazo group, a 4-pivaloylaminophenylazo group, a2-hydroxy-4-propanoylphenylazo group, a phenylthio group, a2-carboxyphenylthio group, a 2-methoxy-5-t-octylphenylthio group, a4-methanesulfonylphenylthio group, a 4-octanesulfonamidophenylthiogroup, a 2-butoxyphenylthio group, a2-(2-hexanesulfonylethyl)-5-tert-octylphenylthio group, a benzylthiogroup, a 2-cyanoethylthio group, a 1-ethoxycarbonyltridecylthio group, a5-phenyl-2,3,4,5-tetrazolylthio group, a 2-benzothiazolylthio group, a2-dodecylthio-5-thiophenylthio group or a2-phenyl-3-dodecyl-1,2,4-triazolyl-5-thio group.
 5. The light-sensitivematerial of claim 3, wherein said divalent group is a substituted orunsubstituted alkylene group, a substituted or unsubstituted phenylenegroup or -NHCOR₇ CONH- where R₇ represents a substituted orunsubstituted alkylene or phenylene group.
 6. The light-sensitivematerial of claim 5, wherein said divalent group is a methylene group,an ethylene group, a 1,10-decylene group, -CH₂ CH₂ -O-CH₂ CH₂ -, a1,4-phenylene group, a 1,3-phenylene group, ##STR21##
 7. Thelight-sensitive material of claim 3, wherein said linking grouprepresented by R¹, R² or R⁶ is a substituted or unsubstituted alkylenegroup, a substituted or unsubstituted phenylene group, -NHCO-, -CONH-,-O-, -OCO- or an aralkylene group.
 8. The light-sensitive material ofclaim 7, wherein said linking group is amethylene group, an ethylenegroup, a 1,10-decylene group, -CH₂ CH₂ OCH₂ CH₂ -, a 1,4-phenylenegroup, a 1,3-phenylene group, ##STR22## -NHCO-, -CONH-, -O-, -OCO-,##STR23## alone or in combination thereof.
 9. The light-sensitivematerial of claim 1, wherein said higher polymer is a homopolymercomprising one or more monomers having the moiety represented by thegeneral formula (I) or a copolymer of at least one monomer having themoiety represented by the general formula (I) with at least oneethylenically unsaturated monomer which does not couple with anoxidation product of an aromatic primary amine developing agent.
 10. Thelight-sensitive material of claim 9, wherein said ethylenicallyunsaturated monomer is acrylic acid, α-chloroacrylic acid, methacrylicacid, acrylamide, n-butylacrylamide, t-butylacrylamide,diacetoneacrylamide, methacrylamide, methyl acrylate, ethyl acrylate,n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutylacrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate,methyl methacrylate, ethyl methacrylate, n-butyl methacrylate,β-hydroxymethacrylate, methylenedibisacrylamide, vinyl acetate, vinylpropionate, vinyl laurate, acrylonitrile, methacrylonitrile, styrene andits derivatives, vinyltoluene, divinylbenzene, vinylacetophenone,sulfostyrene, itaconic acid, citraconic acid, crotonic acid, vinylidenechloride, vinyl ethyl ether, maleic acid, maleic anhydride, maleicesters, N-vinyl-2-pyrrolidone, N-vinylpyridine or 2- or 4-vinylpyridine.11. The light-sensitive material of claim 1, wherein said couplerrepresented by the general formula (I) is selected from the groupconsisting of: ##STR24##
 12. The light-sensitive material of claim 1,wherein said solvent represented by the general formula (II) has aboiling point of about 175° C. or above at atmospheric pressure.
 13. Thelight-sensitive material of claim 1, wherein said alkyl group,cycloalkyl group and alkenyl group represented by R³, R⁴ and R⁵ are eachsubstituted with at least one of a halogen atom, an alkoxy group, anaryl group, an aryloxy group, an alkenyl group and an alkoxycarbonylgroup.
 14. The light-sensitive material of claim 1, wherein said arylgroup represented by R³, R⁴ and R⁵ is substituted with at least one of ahalogen atom, an alkoxy group, an aryloxy group, an alkenyl group, analkoxycarbonyl group or an alkyl gorup.
 15. The light-sensitive materialof claim 1, wherein R³, R⁴ and R⁵, which may be the same or different,each represents a methyl group, an ethyl group, a propyl group, a butylgroup, a pentyl group, a hexyl group, a heptyl group, an octyl group, anonyl group, a decyl group, an undecyl group, a dodecyl group, atridecyl group, a tetradecyl group, a pentadecyl group, a hexadecylgroup, a heptadecyl group, an octadecyl group, a nonadecyl group, aneicosyl group, a 2-ethylhexyl group, a 7-methyloctyl group, acyclopentyl group, a cyclohexyl group, a butenyl group, a pentenylgroup, a hexenyl group, a heptenyl group, an octenyl group, a decenylgroup, a dodecenyl group, an octadecenyl group, or these groupssubstituted with at least one of a fluorine atom, a chlorine atom, amethoxy group, an ethoxy group, a butoxy group, a phenyl group, a tolylgroup, a naphthyl group, or a phenoxy group.
 16. The light-sensitivematerial of claim 1, wherein R³, R⁴ and R⁵, which may be the same ordifferent, each represents a phenyl group, a naphthyl group, a tolylgroup or, these groups substituted with at least one of a fluorine atom,a chlorine atom, a methoxy group, an ethoxy group, a butoxy group, aphenoxy group or an alkyl group.
 17. The light-sensitive material ofclaim 1, wherein R³, R⁴ and R⁵, which may be the same or different, eachrepresents a tolyl group, a 2-ethylhexyl group, a 7-methyloctyl group, acyclohexyl group or a straight chain alkyl group containing 8 to 18carbon atoms.
 18. The light-sensitive material of claim 1, wherein saidsolvent represented by the general formula (II) is selected from thegroup consisting of: ##STR25##
 19. The light-sensitive material of claim1, wherein said solvent represented by the general formula (II) is usedin combination with other high boiling organic solvent selected fromphthalate type solvents, amide type solvents, fatty acid ester typesolvents, benzoate type solvents or phenolic solvents
 20. Thelight-sensitive material of claim 1, wherein the ratio of said solventrepresented by the general formula (II) to said coupler represented bythe general formula (I) is about 0.05:1 to about 20:1 by weight.